Phase transfer of metal cations by induced dynamic carrier agents: biphasic extraction based on dynamic covalent chemistry

In contrast to the classical method where a single molecule is designed to extract metal cations under specific conditions, dynamic covalent chemistry provides an approach based on the implementation of an adaptive dynamic covalent library for inducing the generation of the extractant species. This approach has been applied to the liquid–liquid extraction of copper(ii) nitrate based on a dynamic library of acylhydrazones constituents that self-build and distribute through the interface of a biphasic system. The addition of copper(ii) cations to this library triggers a modification of its composition and the up-regulation of the ligand molecules driven by coordination to the metal cations. Among these, one species has proven to be sufficiently lipophilic to play the role of carrier agent and its formation by component exchange enables the partial extraction of the copper(ii). The study of different pathways to generate the dynamic covalent library demonstrates the complete reversibility and the adaptability of the system. The detailed analytical investigation of the system provides a means to assess the mechanism of the dynamic extraction process.

Phase transfer of Cu(ii) cations is achieved by component exchange in a dynamic covalent library of acylhydrazone ligands. B1/B2 component exchange leads to the generation of a lipophilic carrier agent that extracts Cu(ii) into chloroform.     

Hg2(OH)[BF4], the First Basic Mercurous Tetrafluoroborate

The first basic mercurous tetrafluoroborate, Hg₂(OH)[BF₄], was obtained through a synproportionation reaction of red mercuric oxide, HgO, and elemental mercury in a 35% solution of HBF₄ in water as colourless single crystals. The crystal structure (orthorhombic, Pbca, Z = 8, a = 985.0(1), b = 991.0(1), c = 1141.0(2) pm) contains [(HO)_1/2—Hg—Hg—(OH)_1/2]⁺ zig‐zag chains that are further connected via weak Hg—OH interchain interactions to layers between which the [BF₄]^— are located in an up and down fashion.     

Investigation of the formation process of MCs+-molecular ions during sputtering

In secondary ion mass spectrometry, the detection of MCs+ clusters (with M an element of the specimen) under a Cs bombardment is frequently used for the quantification of major elements. Despite some very good results obtained by this method, some problems still remain. In order to gain some more insight into these problems, the formation mechanism of the MCs+ clusters is investigated using a Monte Carlo model. It is shown that the majority of the constituent particles of the formed clusters are initially first or second neighbor atoms at the surface and that the velocity distribution of the MCs+ clusters becomes broader and peaked at higher velocities with increasing surface binding energy of the M atom. In addition, it is demonstrated that the interaction potential between the M and Cs+ particle has no influence on the velocity distribution of the MCs+ clusters. On the other hand, the cluster formation probability, defined as the probability that a sputtered M and Cs+ particle will form a MCs+ cluster, is extremely sensitive to this interaction potential. It is also shown that the cluster formation probability decreases with increasing surface binding energy. Finally, a good correspondence is obtained between the calculated and experimental velocity distributions of MCs+ clusters sputtered from different monoatomic materials. As a consequence, the Monte Carlo model and the discussed results can be validated.     

Photoelectrochemistry on Ru(II)-2,2'-bipyridine-phosphonate-derivatized TiO2 with the I3-/I- and quinone/hydroquinone relays. Design of photoelectrochemical synthesis cells

Photocurrent measurements have been made on nanocrystalline TiO2 surfaces derivatized by adsorption of a catalyst precursor, [Ru(tpy)(bpy(PO3H2)2)(OH2)]2+, or chromophore, [Ru(bpy)2 (bpy(PO3H2)2)]2+ (tpy is 2,2':6',2' '-terpyridine, bpy is 2,2'-bipyridine, and bpy(PO3H2)2 is 2,2'-bipyridyl-4,4'-diphosphonic acid), and on surfaces containing both complexes. This is an extension of earlier work on an adsorbed assembly containing both catalyst and chromophore. The experiments were carried out with the I3-/I- or quinone/hydroquinone (Q/H2Q) relays in propylene carbonate, propylene carbonate-water mixtures, and acetonitrile-water mixtures. Electrochemical measurements show that oxidation of surface-bound Ru(III)-OH2(3+) to Ru(IV)=O(2+) is catalyzed by the bpy complex. Addition of aqueous 0.1 M HClO4 greatly decreases photocurrent efficiencies for adsorbed [Ru(tpy)(bpy(PO3H2)2)(OH2)]2+ with the I3-/I- relay, but efficiencies are enhanced for the Q/H2Q relay in both propylene carbonate-HClO4 and acetonitrile-HClO4 mixtures. The dependence of the incident photon-to-current efficiency (IPCE) on added H2Q in 95% propylene carbonate and 5% 0.1 M HClO4 is complex and can be interpreted as changing from rate-limiting diffusion to the film at low H2Q to rate-limiting diffusion within the film at high H2Q. There is no evidence for photoelectrochemical cooperativity on mixed surfaces containing both complexes with the IPCE response reflecting the relative surface compositions of the two complexes. These results provide insight into the possible design of photoelectrochemical synthesis cells for the oxidation of organic substrates.     

Synthese und Kristallstrukturen der Phosphanimin-Komplexe MCl2(Me3SiNPMe3)2 mit M = Zn und Co,und CoCl2(HNPMe3)2

Syntheses and Crystal Structures of the Phosphaneimine Complexes MCl₂(Me₃SiNPMe₃)₂ with M = Zn and Co, and CoCl₂(HNPMe₃)₂ The molecular complexes MCl₂(Me₃SiNPMe₃)₂ (M = Zn, Co) have been prepared by the reaction of the dichlorides of zinc and cobalt with Me₃SiNPMe₃ in CH₃CN and CH₂Cl₂, respectively, whereas the complex CoCl₂(HNPMe₃)₂ has been prepared by the reaction of CoCl₂ with NaF in boiling acetonitrile in the presence of Me₃SiNPMe₃. All complexes were characterized by IR spectroscopy and by crystal structure determinations. The complexes MCl₂(Me₃SiNPMe₃)₂ crystallize isotypically. ZnCl₂(Me₃SiNPMe₃)₂: Space group P2₁2₁2₁, Z = 4, 2677 observed unique reflections, R = 0.024. Lattice dimensions at ?70°C: a = 1243.6; b = 1319.0; c = 1464.7 pm. CoCl₂(Me₃SiNPMe₃)₂: Space group P2₁2₁2₁, Z = 4, 3963 observed unique reflections, R = 0,071. Lattice dimensions at ?80°C: a = 1236.3; b = 1317.4; c = 1457.6 pm. CoCl₂(HNPMe₃)₂ · CH₂Cl₂: Space group Pbca, Z = 8, 1354 observed unique reflections, R = 0.055. Lattice dimensions at ?80°C: a = 1247.3; b = 998.4; c = 2882.4 pm. All complexes have monomeric molecular structures, in which the metal atoms are coordinated in a distorted tetrahedral fashion by the two chlorine atoms and by the nitrogen atoms of the phosphaneimine molecules.     

LiTiCl3: Synthesis and thermal behaviour

LiTiCl₃ is obtained as one example within an ample solid solution, Li_24–2nTi_nCl₂₄ (?4?n?10), by synpropotionation of TiCl₃ and Ti in the presence of LiCl (2:1:3 molar ratio) in sealed tantalum tubes at 750°C. It crystallizes with the inverse spinel-type structure according to (Li_0.67)^[4](Li_0.67Ti_1.33)^[4]Cl₄ with, at 25°C, a = 1048.62(4) pm, space group Fd3m. Thermal expansion is linear with α = 4.85 × 10^?5K^?1 up to about 300°C and thereafter, when the migration of Li⁺ from tetrahedral to octahedral interstices becomes increasingly important, it exhibits a relative decrease resulting, finally, in the phase transition to a NaCl-type structure that is observed for the first time at about 575°C.     

Übergangsmetall-substituierte phosphane,arsane und stibane : XXV. C5H5(CO)2[P(OMe)3]M-substituierte dioxaphospholane und dioxarsolane; stereochemische evidenz für den intermolekularen ablauf einer isomerisierung unter methylgruppenverschiebung

2-C₅H₅(CO)₂[P(OMe)₃]Mo(W)-substituted 4,4,5,5-tetramethyl-1,3,2-dioxarsolanes and -dioxaphospholanes (Ia–Ic) are obtained from C₅H₅(CO)₃M derivatives via CO/P(OMe)₃ exchange. In all cases the phosphite ligand appears trans to the σ-bonded arsenic heterocycle, which prefers a conformation with the transition metal group in an axial position. The dioxaphospholane-metal (Ia) undergoes isomerization with alkyl migration at 0°C, which due to stereochemical reasons can only occur by an intermolecular mechanism.     

Zum thermischen Verhalten von Li3MnO4. II [1, 2]. Über α- und β- Li2MnO3

Thermal Behaviour of Li₃MnO₄. II. α- and β-Li₂MnO₃ By thermal decomposition of Li₃MnO₄ we obtained two new forms of Li₂MnO₃: α-Li₂MnO₃ crystallizes due to Guinier-Simon photographs cubic face-centered with a = 4.09₂ Å, β-Li₂MnO₃ hexagonal with a = 4,93, c = 14.24 Å, c/a = 2.89. α-Li₂MnO₃ is paramagnetic with μ = 3,82 B.M. Below the Neel temperature (≈? 50 K) β-Li₂MnO₃ is antiferromagnetic. Effective Coordination Numbers, ECoN, are calculated and discussed.     

Isolation,identification and synthesis of the sex pheromone of the citrus mealybug,Planococcus citri (risso)

The sex attractant pheromone of the citrus mealybug, $\text{Planococcus citri}$ (Risso), has been Identified as (1$\text{R}$-$\text{cis}$)-(+)-2,2-dimethyl-3-(1-methylethenyl)cyclobutanemethanol acetate (VI).     

Non-radioactive determination of PTH and dabsyl phosphoamino acids by capillary electrophoresis

Summary Capillary electrophoresis is a novel technique in the non-radioactive determination of phosphoamino acids. The main advantage of the method presented is the high selectivity and the ability to separate all phosphoamino acid derivatives. Non-radioactive determination of PTH or dabsyl phosphoamino acids by capillary electrophoresis provides a fast and simple screening procedure for all O-phosphorylated amino acids in protein and peptides in the low picomolar range.